Absorbent and process for preparation thereof



Patented Jan. 5, 1954 UNITED STATES PATENT OFFICE ABSORBENT- AND PROCESS FOR PREPARATION THEREOF JohnB. Buffett,"Media, Pa' ja'ssign'or to Atta'pul- "gus Minerals and Chemicals Corporation, Philadelphia, Pa., a "corporation of Maryland No. Drawing. 4 Application-March 18, 1953, Serial No. 343,250

'IG'Claims. (01. 252-449) 1 This invention relates to improvements in clay materials for absorbing oil, grease, water, and the like, and more particularly to a highly absorbent material composed of clay of the attapulgite type, and especially Georgia-Florida processes. The resulting product is adapted among other uses as a floor clearner whereby oil, grease, water, and the like will be absorbed by the clay to keep the floor free of undesirable fluids. While such attapulgite clay of increased absorbency is a satisfactory and usefulabsorbent material for many purposes, it is desirable to further increase the absorbency thereof so that 1 a smaller amount of such material may be required for a particular purpose than has been required heretofore.

Applicant has discovered that a highly absorptive and relatively hard material may be formed by compounding an attapulgite type clay, especially Georgia-Florida fullersearth, which has not been dried to a V. M. contentbelow with a cement or other cementitious material which will produce a basic water extract and in a ratio of clay'to cement of from 2:1 to :1. The improved clay material has an absorbency greatly in excess of attapulgite treated in accordance with methods heretofore employed for improving the absorptivity of clay, and in addition is of sufiicient hardnessto be adaptedfo'r use in all processes in which clay absorbents are commonly employed. It is especially adapted for use asa fioor cleaner, which requires that the absorbent material be sufficiently hard as to withstand, without substantial breaking or crumbling. the weight of a person.

The only clays which are suitable for producing the improved absorptive material in accordance with this invention are those of the attapulgite type. Georgia-Florida fullers earth is particularly suitable for this purpose.

As above pointed out, mixed with the attapulgite clay is a cement or other cementitious "with'a clay ratio of 5:1. variations in the amount of cement have only small effect upon the quality of the product. However, as the proportion of cement is increased'the absorbency'increa'ses whilethe hard- .ness decreases.

materiahwlii'ch will'yield a basicsolution when extracted with water. A natural cement, a p02- z'o'lona cement, "or Portland cement, or any other common type of'cement may be employed; however, 'Portland cement is especially suitable.

"Othercemerititious materials which may be used include calcium oxide, magnesium oxide, and all other common limes, and also the hydraulic limes. Of these, however, calcium oxide is preferred. g

"The amount of cementitious material "added should be such "that the ratio of clay to cement isfrom 2:1 to 20:1, andlpr'eferably from 3:1'to '10:1, especially good products being obtained Within those limits,

The absorbentmaterials produced in accordance with this invention are greatly increased in absorbency over the heretofore known clay absorbents. By Way of comparison, whereas at tapulgite treated by conventional methods has a maximum oil retention of from to 80, the

absorbent'material produced'in accordance with :this invention may possess an oil retention of about and higher. Moreover, an improved absorbent material of this invention, having 'a V. M. content of not more than 40 is characterizedby an absorbency greatly in excess of eitt'apulgite clay having a corresponding V. M. content and treated inaccordance with methods heretofore employed for improving the absorptivity of clay. 'The "oil retention values set forth herein were determined by the following procedure: a -5G-'gram sample of the absorbent is placed in *a 500-ml. beaker and covered completely with oil having the following characteristics: gravity, 217 A. P. I.; viscosity at 100 F. of 557, and-at 210 F. of 5 2.6 Saybolt seconds universal. After standing for 15 minutes to soak, the "mixture is stirred to assure complete wetting. The mixture is transferred to a 111 mm. I. D. Buchner funnel and filtered through a No. 42 filter'pap'er for two hours under 12-inch vacuum and at a temperature of from to F. Finally, theabsorbent cake is removed from the funnel and weighed. The increase in weight of absorbent sample expressed as per cent of the tion-va-lue. It is recognized in the art that the 3 ability of a material to absorb oil is also an indication of absorptivity to other fluids.

The improved absorbents further are sufiiciently hard so as to be suitable for use in substantially all processes employing conventional clay absorbents. For use as a floor cleaner and for most other conventional uses, it is essential that the absorbent possess a hardness value determined by the method below set forth in excess of 60. The absorbents of the present invention range from about 65 to 80 or more.

In describing the method employed for determining hardness of an absorbent, the mesh of the absorbent will be assumed to be 10/60, that is, the absorbent will pass through a 10 mesh standard Tyler screen but will be retained by a 60 mesh screen. It is to be understood, however, that the method is equally adapted for other mesh material.

A 50-gram sample of the absorbent is placed in the pan of a Ro-Tap testing screen shaker, together with ten steel balls. The pan is placed in the usual manner in the Ro-Tap shaker. Also inserted in the shaker is a 60 mesh retaining or limiting screen. With the hammer plate in place, but without the hammer operating, the Ro-Tap shaker is placed into operation and allowed to run for 30 minutes. The absorbent then is transferred from the pan to the limiting screen and the Ro-Tap shaker again operated for 5 minutes with the hammer operating to tap the screen and with the pan in position to catch the absorbent passing through the screen. Finally, the portion of absorbent remaining on the screen and the portion of the absorbent passing through and into the pan are Weighed separately. The weight of the fraction retained on the screen expressed as per cent of the combined weight of the two portions is designated as the hardness value.

In accordance with this invention, the improved absorbent is prepared by first adding together the cementitious material which, as above mentioned, is of the type capable of giving a basic solution when extracted with water, and attapulgite clay which has not been dried to a volatile matter (referred to hereinafter as V. M.) content below 10%. The cementitious material and attapulgite clay are added together in amounts such that the ratio of clay to cementitious material is in the range of from 2:1 to 20:1. In order to produce the novel absorbent, it is essential that the clay not be dried to a V. M. content below 10% before mixing the clay with the cementitious material. Thus the clay used in this invention may be raw attapulgite clay or attapulgite clay which has been partially dried but not below 10% V. M. Calcination or activation of attapulgite clay to a V. M. below 10% which results when clay is heated to a constant weight at temperature above about 350 F., destroys the colloidal properties of attapulgite clay as is well known in the art and renders it unsuitable for use in the subject invention. Water is then added to the mixture to raise the V. M. content thereof to at least 60% after which the mixture is pugged, stirred, agitated, or otherwise mixed to obtain a uniform distribution of the ingredients. It is important to note that the clay and cementitious material cannot be mixed in the dry form or in the presence of only a small amount of water but it is necessary to have sufficient water present during the mixing operation to produce a, mixture having a V. M. content, as

above mentioned, of at least 60%. It has been found that the more water that is present, the better the results. Thus, while the mixture may contain only about 60 to water and the mixing step formed by pugging, a superior product may be obtained by adding suflicient water to produce a, thin slurry of the clay and cementitious material which may be simply stirred to obtain the desired uniformity of distribution.

In the event it is desired to accomplish the mixing of the clay and cementitious material by pugging, the water is added in an amount sufficient to raise the V. M. content of the mixture of from 60 to about 75%. Following the pugging step, it is preferable, although not necessary, to extrude the mixture by means of any commercial extruder. The primary purpose of extrusion is to form the material into a convenient shape for drying and therefore extrusion may be eliminated if desired. If the material is to be extruded, however, it is preferable that the V. M. content of the clay-cement mixture be at the highest value consistent with the extrusion operations and with the ready handling of the material. Thus, the amount of water added to the mixture should be as high as possible without making the mixture too soft for handling and extrusion. This condition may be readily determined by observation and inspection.

In the event that it is desired to perform the mixing operation by stirring, sufl'icient water should be added to form a thin slurry. Uniformity in the mixture usually is obtained with 30 to 60 minutes of mixing.

The uniform mixture finally is treated in any suitable manner to remove sufiicient Water to increase the absorptivity of the clay to a desired level. The V. M. content of the final product is not critical and it has been found that an absorbent material produced in accordance with this invention having a V. M. content of 40% or less will possess a markedly higher absorptivity than attapulgite clay having a corresponding V. M. content and treated in accordance with methods heretofore employed for improving the absorptivity of clay. Although the V. M. content of the improved absorbent material is not critical, it is to be understood that the lower the V. M. the higher the absorptivity and that best results are obtained by reducing the V. M. of the product to about 5 to 10%.

In removing the Water from a clay-cement mixture which has been pugged and if desired extruded, the mixture simply is placed in a convenient drier or kiln and dried preferably under mild drying conditions at a temperature, for example, of about 500 to 750 F. and for a period sufficient to reduce the V. M. content of the mixture to the desired level. In removing the water from a thin slurry of clay and cement which has been mixed simply by stirring or agitating in a suitable mixer, it is preferred to dewater the slurry by filtration, evaporation, or other suitable method following which the material is dried in an oven or kiln, as hereinbefore described.

The dried product, if desired, may be ground to any size suitable for a particular application or use.

It has been found that a somewhat higher oil retention value of the improved absorbent may be obtained by allowing the material to age before drying for a, period of a few hours up to two days. No further significant increase will be real ized by more prolonged aging.

The following procedure waszemployed for determining the V. M. content. ofthe'various clays and mixtures as set forth. herein. An. accurately weighed to G-gram sample of the material is heated in an electric oven at 220 F. for two hours. Thereafter, the sample is heated in a muffle furnace at a temperature of from 1700L1800 F. for 30 minutes. The sample is again weighed, after cooling to room temperature in a desiccator. The decrease in weight of the sample expressed. as per cent is referred to as the V. M. content.

Within. the clay cement. ratio range of this invention, that is, from 2:1 to 20:1, only minor differences are noted. in. the .absorptivity and hardness of the product. In most cases the improved attapulgite absorbent has a minimum hardness of about 65 and oil retention value of about 120'or more. The hardness decreases and the absorbency increases slightly as the proportion of cement is increased.

To facilitate the understanding of this invention, the following examples are given by way of illustration.

In Examples I to III, inclusive, the attapulgite clay employed was obtained from an area near Quincy, Florida, and had the following chemical analysis:

Weight percent (volatile free basis) A series of mixtures of Portland cement and attapulgite clay, which clay had an oil retention value of approximately 80 after drying for 30 minutes at 750 F., were made up. The. mixtures contained varying clay-cement ratios. For two minutes each mixture was pugged in a pug mill and then suiiicient Water was added to bring the V. M. content up to either 65 or70. The mixture was pugged for an additional eight minutes. After permitting itto age for two'days, the mixture was extruded through a l-inch thick, A-inch' straight hole die. Finally, the extruded material was dried in a rotary furnace for 30 minutes at 750 F. By means of a roller mill the absorbent product was ground to /60 mesh. In the table following, the oil retention,

and hardness values are given for the various ratios of clay to cement in the absorbent.

It will be noted that oil retention decreasesand hardness increases as the clay-cement ratio increases. Similar effects upon the final absorbent product result as the V. M. content of the mixture during extrusion is decreased.

' Example II In-this case, Example I was repeated except that the aging stepwas: omitted and immediately after the second pugging operation, the mixture Extrusion V. M. 65 Extrusion V M. 70. Ratio, claty/ semen g Hardness 9 55 5? Hardness It will benoted by. comparison ofthe results of Examples I and II that aging slightly improves the oil retention property of the absorbent product.

Example III In this case, Example II was repeated except that the drying temperature was reduced to 500" F. In the following table the oil retention and hardnessvalues are given for various clay- By comparison of the results of Examples II and III, it will be seen that slightly. higher oil retention values of the product are realized when drying is carried on at higher temperatures.

In Example IV, the attapulgite clay employed was obtained from an area near Amsterdam, Georgia, and had the following chemical analysis:

Weight percent .(volatile free basis) S10: 65.0 FezO3 3.9 T102 0.3 Al203 11.6 CaO 2.8. MgO 10.6 Undetermined 5.8

Example IV A series of mixtures having a clay-cement ratio of 5: 1 were made up by individually mixing with such clay, having an oil retention value after calcination for 30 minutes at 750 F. of 80.4, several cementitious materials which give basic water extracts. Each mixture was pugged in a pug. mill for two minutes and then sufiicient water was added to bring the V. M. content approximately upto the maximum for extrusion, i. e., about 65-75. The mixture was p-ugged for an additional eight minutes. Immediately there-' after the mixture was extruded. Finally, the extruded material was dried in a rotary. furnace for 30 minutes at 750 F. By means of a roller Cementitious additive 63; Hardness Portland cement (VM 70) 147 66 Quick lime (VM 73) 130 Hydrated calcium lime (VM 73). 139 67 Dolomitic quick lime (VM 66)..- 122 57 High mag. hydrated lime (VM 73 137 71 Calcium aluminate cement (VM 70) 129 72 Example V This example was carried out to demonstrate that attapulgite clay which has been dried or calcined to a V. M. less than is unsuitable for the purposes of this invention.

Clay-cementitious material mixtures were made up by mixing separately substantially equal amounts (on V. F. basis) of raw attapulgite clay having a V. M. of 50% and of attapulgite clay (2% V. M.) calcined at 1100 F. either with Portland cement or with a saturated water solution of sodium silicate, as set forth in the table below. To each mixture (except the last) sufficient water was added to give a V. M. of 65% and then the mixture was agitated in a pug mill for 30 minutes. Where possible the pugged mixture was extruded. Each mixture thereafter was dried at a temperature of 700 F. and ground to 10/60 mesh. The oil retention ability for each mixture was determined and the results are given in the table below.

From the results set forth in the table above, it will be apparent that the products produced in accordance with this invention from raw attapulgite clay possess very excellent oil retention characteristics, whereas mixtures of attapulgite clay having less than 10% V. M. and cement or sodium silicate have very low oil retention values.

Example VI 5000 grams of raw attapulgite clay having a V. M. of 48.5% were pugged with 530 grams of Portland cement. After mixing in a pug mill for 2 minutes, sufficient water was added to in crease the V. M. of the mixture to 68.6%. Mixing was continued for minutes and then the mixture was extruded through a die plate having diameter straight holes. The extrudate was collected and portions thereof were dried to various V. M. contents as shown in the table below. Each portion was separately ground to yield a 10/60 mesh product. The oil retention value of each sample in weight per cent was determined and the results are presented in the following table.

Cfl

8 OIL RETENTIONS OF INIPROVED CLAY- CEMENT ABSORBENT AT VARIOUS CON- DITIONS OF FINAL DRYING Volatile Attapulgus matter oil retencontcnt tions, Portion No. alter final weight drying, percent weight oll re percent talned l. 6 132. 5 5. 2 133. 8 l0. 6 120. 6 18. 7 108. 4 33. 5 65. l 42. 5 33. 3

The data presented in the table above shows that an absorbent composition produced in accordance with the subject invention and having a V. M. content of 40% or less is operable as an absorbent and specifically that the oil retention value varies from about 33% where the final V. M. is approximately 40% to an oil retention value in excess of where the final V. M. is 1.6%.

While the preferred embodiments of the invention have been described, it is to be understood that minor changes may be made in the details 0f preparation of the absorbent without departing from the spirit and scope of the invention as defined by the appended claims.

I claim:

1. An absorbent composition formed by mixing a major proportion of attapulgite clay, which has not been dried to a V. M. content below 10%, with a minor proportion, sufficient to increase the absorptivity of said clay, of a cementitious material which will yield a basic water extract and selected from the group consisting of an alkaline earth metal silicate, oxide, and hydroxide, in the presence of sufficient water to produce a mixture having a V. M. content of at least 60%, and drying said mixture sufficiently to increase the absorptivity of said clay.

2. An absorbent composition formed by mixing a major proportion of raw attapulgite clay with a minor proportion, sufficient to increase the absorptivity of said clay, of a cementitious material which will yield a basic water extract and selected from the group consisting of an alkaline earth metal silicate, oxide, and hydroxide, in the presence of sufficient water to produce a mixture having a V. M. content of at least 60%, and drying said mixture sufficiently to increase the absorptivity of said clay.

3. An absorbent composition formed by mixing a major proportion of attapulgite clay, which has not been dried to a V. M. content below 10%, with a minor proportion, sufficient to increase the absorptivity of said clay. of a cementitious material which will yield a basic water extract and selected from the group consisting of an alkaline earth metal silicate, oxide, and hydroxide, in the presence of sufficient water to produce a mixture having a V. M. content of at least 60%, and drying said mixture to a V. M. content of not more than 40% 4. An absorbent composition formed by mixing attapulgite clay, which has not been dried to a V. M. content below 10%, with a cementitious material which will yield a basic water extract and selected from the group consisting of an alkaline earth metal silicate, oxide, and hydroxide, in a clay-cementitious weight ratio of from 2:1 to 20:1 and in the presence of sufficient water to produce a mixture having a V. M. content of at least 60% and drying said mixture suificiently to increase the absorptivity of said clay.

5. An absorbent composition formed by mixing attapulgite clay, which has not been dried to a V. M. content below with Portland cement in a clay-cement weight ratio of from 2:1 to 20:1 and in the presence of sufficient water to produce a mixture having a V. M. content of at least 60% and drying said mixture sufiiciently to increase the absorptivity of said clay.

6. An absorbent composition formed by mixing attapulgite clay, which has not been dried to a V. M. content below 10%, with Portland cement in a clay-cement weight ratio of from 3:1 to 10:1 and in the presence of sufiicient water to produce mixture having a V. M. content of at least 60% and drying said mixture suificiently to increase the absorptivity of said clay.

7. An absorbent composition formed by mixing attapulgite clay, which has not been dried to a V. M. content below 10%, with calcium oxide in a clay-calcium oxide weight ratio or" from 2:1 to 20:1 and in the presence or" sufiicient water to produce a mixture having a V. M. content of at least 60% and drying said mixture sufiiciently to increase the absorptivity of said clay.

8. An absorbent composition formed by mixing attapulgite clay, which has not been dried to a V. M. content below 10%, with calcium oxide in a clay-calcium oxide weight ratio of from 3:1 to 10:1 and in the presence or sufficient water to produce a mixture having a V. M. content of at least 60% and drying said mixture sufficiently to increase the absorptivity of said clay.

9. A. process for producing an improved absorbent composition comprising mixing a major proportion of attapulgite clay, which has not been dried to a V. M. content below 10%, with a minor proportion, sufl'icient to increase the absorptivity of said clay, of a cementitious material which will yield a basic water extract and selected from the group consisting of an alkaline earth metal silicate, oxide, and hydroxide, in the presence of sufficient water to produce a mixture having a V. M. content of at least 60%, and drying said mixture sufficiently to increase the absorptivity of said clay.

10. A process for producing an improved absorbent composition comprising mixing a major proportion of raw attapulgite clay with a minor proportion, sufficient to increase the absorptivity of said clay, of a cementitious material which will yield a basic water extract and selected from the group consisting of an alkaline earth metal silicate, oxide, and hydroxide, in the presence of sufficient water to produce a mixture having a V. M. content of at least 60%, and drying said mixture sufficiently to increase the absorptivity of said clay.

11. A process for producing an improved absorbent composition comprising mixing a major proportion of attapulgite clay, which has not been dried to a V. M. content below 10%, with a minor proportion, suflicient to increase the absorptivity of said clay, of a cementitious ma- .terial which will yield a basic water extract and selected from the group consisting of an alkaline earth metal silicate, oxide, and hydroxide, in the presence of sufiicient water to produce a mixture having a V. M. content of at least 60%, and drying said mixture to a V. M. content of not more than 12. A process for producing an improved absorbent composition comprising mixing attapulgite clay, which has not been dried to a V. M. content below 10%. with a cementitious material which will yield a basic water extract and selected from the group consisting of an alkaline earth metal silicate, oxide, and hydroxide, in a clay-c-ementitious weight ratio of from 2:1 to 20:1 and in the presence of sufficient water to produce a mixture having a V. M. content of at least and drying said mixture suificiently to increase the absorptivity of said clay.

13. A process for producing an improved absorbent composition comprising mixing attapulgite clay, which has not been dried to a V. M. content below 10%, with Portland cement in a clay-cement weight ratio of from 2:1 to 20:1 and in the presence of sufiicient water to produce a mixture having a V. M. content of at least 60% and drying said mixture sufiiciently to increase the absorptivity of said clay.

14. A process for producing an improved absorbent composition comprising mixing attapulgite clay, which has not been dried to a V. M. content below 10%, with Portland cement in a clay-cement weight ratio of from 3:1 to 10:1 and in the presence of sufficient water to produce a mixture having a V. M. content of at least 60% and drying said mixture sufiiciently to increase the absorptivity of said clay.

15. A process for producing an improved absorbent composition comprising mixing attapulgite clay, which has not been dried to a V. M. content below 10%, with calcium oxide in a clay-calcium oxide weight ratio of from 2:1 to 20:1 and in the presence of sufficient water to produce a mixture having a V. M. content of at least 60% and drying said mixture sufliciently to increase the absorptivity of said clay.

16. A process for producing an improved absorbent composition comprising mixing attapulgite clay, which has not been dried to a V. M. content below 10%, with calcium oxide in a clay-calcium oxide weight ratio of from 3:1 to 10:1 and in the presence of sufficient water to produce a mixture having a V. M. content of at least 60% and drying said mixture sufficiently to increase the absorptivity of said clay.

JOHN B. BUFFETT.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,249,681 Briggs et a1 July 15, 1941 2,363,876 La Lande Nov. 28, 1944 2,409,263 Ewing et a1. Oct. 15, 1946 

11. A PROCESS FOR PRODUCING AN IMPROVED ABSORBENT COMPOSITION COMPRISING MIXING A MAJOR PROPORTION OF ATTAPULGITE CLAY, WHICH HAS NOT BEEN DRIED TO A V. M. CONTENT BELOW 10%, WITH A MINOR PROPORTION, SUFFICIENT TO INCREASE THE ABSORPTIVITY OF SAID CLAY, OF A CEMENTITIOUS MATERIAL WHICH WILL YIELD A BASIC WATER EXTRACT AND SELECTED FROM THE GROUP CONSISTING OF AN ALKALINE EARTH METAL SILICATE, OXIDE, AND HYDROXIDE, IN THE PRESENCE OF SUFFICIENT WATER TO PRODUCE A MIXTURE HAVING A V. M. CONTENT OF AT LEAST 60%, AND DRYING SAID MIXTURE TO A V. M. CONTENT OF NOT MORE THAN 40%. 